Interpolymers from haloaryl phosphorous thiodihalide



United States Patent M 3,294,745 INTERPOLYMERS FROM HALOARYL PHQSPHOROUS THIODIHALIDE Marco Wismer, Gibsonia, Pa., assignor to Pittsburgh Plate Glass Company, Pittsburgh, Pa., a corporation of Pennsylvania No Drawing. Filed Feb. 16, 1962, Ser. No. 173,823 Claims. (Cl. 260-47) This invention relates to novel monomers and interpolymers, and pertains more specifically to monomers obtained by the reaction of halogenated mononuclear aromatic compounds with phosphorus trihalides and sulfur, and to interpolymers of such novel monomers with polyhydroxy aromatic compounds.

It has been discovered that halogenated mononuclear aromatic compounds having at least one carbon atom of the aromatic ring available for reaction will react with phosphorus trihalides and sulfur in the presence of a Friedel-Crafts catalyst to give novel monomeric compounds substantially in accordance with the following equation:

R XH+PX +S R Friedel- Crafts catalyst wherein X is a halogen radical selected from the class consisting of chlorine, bromine and fluorine, R is an alkyl group containing from about 1 to 6 carbon atoms, n is a whole number from 1 to 5, and m is a whole number equal to one or zero, and the sum of m plus It does not exceed 5.

For example, when monochlorobenzene and phosphorus trichloride are utilized along with sulfur as the reactants, the resulting product is monochlorophenyl phosphorus thiodichloride.

The product depicted above will condense with nonadjacent polyhydroxy aromatic compounds, liberating hydrogen chloride and forming resins of the linear polymer type, when mixtures of these compounds are subjected to elevated temperatures. Resinous materials produced from the hereinabove described monomers have excellent fiber-forming properties.

The reaction for producing the linear type polymer may be illustrated by the following equation, wherein p-chlorophenyl phosphorus thiodichloride and 2,2-bis(4-hydroxyphenyl) propane are utilized as illustrative reactants:

All 01 wherein the bracketed portion of the structure is the repeating unit.

3,294,745 Patented Dec. 27, 1966 The novel haloaryl phosphorus thiodihalide monomers described herein can be prepared as depicted in reaction 1) above wherein the halogenated mononuclear aromatic compound utilized as one of the reactants may be monochlorobenzene, monobromobenzene, monofluorobenzene, dichlorobenzene, trichlorobenzene, tetrachlorobenzene, pentachlorobenzene, di-bromobenzene, tribromobenzene, tetrabromobenzene, pentabromobenzene, difluorobenzene, trifluorobenzene, tetrafluorobenzene, pentafluorobenzene, monochloroto'luene, monobromotoluene, monofluorotoluene, dichlorotol-uene, trichlorotoluene, tetrachlorotoluene, dibr omotoluene, tribromotoluene, tetrabromotoluene, difiuorotoluene, trifluorotoluene, tetrafluorotoluene, monochloroethylbenzene, monochloropropylbenzene, monochlorobutylbenzene, monochloroamylbenzene, monochlorohexylbenzene, monobromoethylbenzene, dibromoethylbenzene, tribromoethylbenzene, tetrabromoethylbenzene, difluoropropylbenzene, difluorobutylbenzene, difluoroamylbenzene, difiuorohexylbenzene, and the like, and wherein the phosphorus trihalide may be phosphorus trichloride, phosphorus tribr-omide or phosphorus trifluoride.

The reaction of -a haloaryl compound with a phosphorous trihalide and sulfur in accordance with this invention can readily be effected by heating a mixture of the reactants in the presence of a Friedel-Crafts catalyst such as aluminum chloride, ferric chloride, stannic chloride, boron trifluoride, zinc chloride, antimony pentachloride, titanium chloride, hydrofluoric acid, sulfuric acid, phosphoric acid, phosphorous pentoxide, bismuth chloride and telluriu-m diand tetrachlorides and the like. The Friedel-Crafts catalysts are discussed in detail in volume 3 of Organic Reactions (1946), pages 2 to 4.

One preferred method of producing the hereinabove described novel haloaryl phosphorous thiodihalides comprises reacting an excess of a phosphorous trihalide with a haloaryl compound in the presence of a Friedel-Crafts catalyst at temperatures of about 60 C. to C., although temperatures of 35 C. or lower to C. or higher can also be utilized. The product of this reaction is a haloaryl phosphorous dihalide. Sulfur is then added to the reaction mixture and exothermal-ly reacts with the haloaryl phosphorous dihalide to form a haloaryl phosphorous thiodihalide.

As indicated in the graphically represented reaction hereinabove, equimolar quantities of reactants are required stoichiometrically to produce an equivalent number of moles of the haloaryl phosphorous thiodihalide. However, no particular ratio of reactants is required to effect the reaction or reactions. Thus, any one or two, of the reactants may be used in excess of 5 to 1, or

higher, in relation to the remaining reactants or reactant. Y

The quantity of Friedel-Crafts catalyst utilized is not critical and may be varied widely. In general, it is preferable to employ form about 10 percent to 200 per cent by weight of catalyst based on the total weight of the haloaryl reactant. Amounts of catalyst smaller than 10 percent or larger than 200 percent, however, may be utilized if desired.

Recovery of the desired product from the reaction mixture can be accomplished by the following procedure:

(1) Distilling the mixture at reduced pressure to remove excess phosphorous trihalide,

(2) Washing the distilland with ice water to remove residual Friedel-Crafts catalyst,

(3) Solubilizing with a solvent such as lactol spirits of naphtha, monohalobenzene, and the like.

(4) Washing of the solution with water, accompanied by phase-separation of the solution-phase from the waterphase,

3 (5) Drying with calcium chloride or similar desiccant, (6) Filtering of the solution, and (7) Distilling.

The oily product obtained by the above procedure may Example 1 The following ingredients were admixed in a flask equipped with a stirrer, thermometer and condenser:

be further purified by fractional distillation at reduced 5 Grams r ar hliliri liil iiiiirirag s32 sis-213:2; 5328 t io i ai ein iqui orm.

While the above described method for recovering the Alumlmlm Chloride g 320-0 reaction product is very efiective, other methods of recevering the product, for example, selective solvent ex- 10 wil 5 :12: w gii gzy c ig g e c hg gzi traction, may be employed if desired. The haloaryl phosphorous thiodihalide compounds pro- 'g teh g e gas rapldly g ifigz i hggg zgg duced by the above procedure are useful as monomers th f E ht (180) rams which can be condensed with non-ad acentpolyhydroxy 15 f 3P d 0 i f p :13 d 1: til g tY T? r aromatic compounds liberating hydrogen halide and form- 0 h hr were a e 0 e 3 d e d ing resins from which fine fibers of remarkable strength 2:23; 5 22 i fi g h i gzg z gg i i gg i can be drawn. 0 The condensation type polymerization of the herein- 2?; $5 2 held at thls temperature for a Period above described monomers generally requires the exposure of the admixed monomers to elevated temperatures, The g g h ig: was i g ggg i g d about 70 C. to about 220 C., for a prolonged period f an emPe hre 0 are atheists: assesses: sesame; tion 0 re u e ressure, own to mi imeters o mercury, during the condensation reaction is advantageous. 25 washing the disthlahd with i e water- The Product was The solid reaction product which is obtained may be purig efthacted wlth 2 2 splntls tQ p g l E g p maeasoutrze:

y u filtered; yielding a colorless, clear solution. (1) Solubrhzahon in a suitable solvent such as acetone, The naphtha Solvent was removed by distilling the e f the clear solution obtained above at reduced pressure. One (2) Fhtraheh to remeve heh'sohlble matter, and hundred and thirteen and eight-tenths (113.8) grams of (3) Recovery of a sol1d resinous product by removal of ayenow hazy, Oily product were obtained the solvent by dlstlhahoh or evaporahoh- The product was further purified by distillation where- A th d-ace t 01 h dmx aromatic m0n0 in the fraction boiling above 107 C., vapor temperature, g g L 2 zvith g haloaryl phos 35 at 0.8 millimeter of mercury, was retained and redistilled. phorous thiodihalides obtained by the reaction of this fi f f i g gg g tig isf g g gggg e t gggg z ii invent'on, are the follow" r e (a) Non-adjacent po l yiydroxy mononuclear rare. 4 0.7 millimeter of mercury, was retained and further (115- matic hydrocarbons such as resorcinol, methylresorcinol, 40 e From the third e the fraehoh whleh hixylresorcinol, hy-droquinone, Phloroglucinol, and the zl r it z gr e iuig g of lleiifi 53 52? 1 Nomadjacent Polyhydroxy aromatic compounds lected as product. The total weight of this fraction was With condensed ring systems such as 1,4-dihydroxynaph- P th alene, 1,S-dihydroxynaphthalene, 1,7 dihydroxynaphtha- A Inlcfoanalysls 0f the Product Was Compared Wlth the lene, 9,10-dihydroxyanthracene, 1,3,6-trihydroxynaphthatheoretical composition of monochlorophenyl phosphorus lene, and the like; thiodichloride, as indicated below:

Percent Percent Percent Percent Percent Carbon Hydrogen Chlorine Sulfur Phosphorous Theoretical Value 29. 33 1. 64 43. 35 13. 05 12. 61 Experimental Value 29. 10 1. 46 43. 20 13. 30 12. 47 D0 29. 19 1. 5s 43. 42 13.36 12. 54

(c) Polyhydroxy aromtic compounds with separated Example 11 rin systems such as 2,2-bis(4-hydroxyphenyl)propane, one hundred thin y four and five-tenths. (134.5) grams hydrXYPh%nY1)efl-1ane 11'b1s(4 hydroxy' (0.55 gram-mole) of material, prepared in the manner of phenynlsobutane zz'bls(4'hydroxyphenynbuthne Example I and identified as monochlorophenyl phosb1s(4 hydroxyfz'methylphenyl)Propane phorus thiodichloride, were admixed with 114.0 grams droxy 2 tertlarybutwphenyl)propane 1715(2 hydhoxye (0.5 gram-mole) of 2,2-bis(4-hydroxyphenyl)propane in naphthynmethane f 'dlhydmxybenmphtncner X' a glass vessel equipped with stirrer, thermometer, inert droxydiphenyl, 4,4 hydroxy-3,3 -methyl1d1phenyl, 4,4 gas purge and reflux condenser Y "P Y f f The mixture was heated and stirred for 52 hours at dlphenyl f i h e the atmospheric pressure, resulting in the evolution of hydro- The following examples illustrate in detail the preparagen chloride gas The temperature was elevated from tion of novel haloaryl phosphorous thiodihalide monoto during this time f and the Polymerization of Such mpnomers to P P For an additional 92 hours the mixture was heated rp y r The examples are not intended to 1mm and stirred under reduced pressure, 10 millimeters of Hg the invention, however, for there are, of course, numerous to 2 millimeters of Hg. Hydrogen chloride gas continued possible variations and modifications. 75 to evolve and the temperature was elevated from 200 C.

to 220 C. The heating was then discontinued and the reaction product was allowed to cool.

The solid reaction product was solubilized with acetone and filtered. The acetone solvent was evaporated, leaving a solid resinous residue having a softening point of 55 C. At 80 C. it was a viscous liquid having suflicient cohesiveness to cure a thin filament to be drawn from the surface of the material. At 87 C. the copolymer was very soft and at 120 C. it was liquid.

Example 'III The following ingredients were admixed in a flask equipped with a stirrer, thermometer and condenser:

Grams Monobromobenzene (1.0 gram-mole) 157.0 Phosphorus trichloride (3.0 gram-mole) 413.0 Aluminum chloride (1.0 gram-mole) 133.3

The above mixture was agitated and heated at reflux temperature, about 80 C., for about 8 hours. Hydrogen bromide gas rapidly evolved during this period. The mixture was then cooled to about 30 C. and 33 grams of sulfur were added. Heat was applied and the mixture exothermed to 57 C. The temperature of the mixture was raised to 80 C. and maintained there for a period of about 5 minutes.

The resulting mixture was distilled at reduced pressure and a pot temperature of 75 C. to 80 C. for 30 minutes to remove excess phosphorus chloride, after which theresidual aluminum chloride was removed by washing the distilland with ice water. The product was then extracted with monobromobenzene. The monobromobenzene solution was washed several times with water and subsequently phase-separated from the water. I

The monobromobenzene solvent was removed by distilling the solution obtained above at reduced pressure. Eighty one and three-tenths (81.3) grams of dark brown, cloudy liquid were obtained.

The product was further purified by distillation, wherein the fraction boiling above 62 C., vapor temperature, at 0.7 millimeter of mercury was retained and redistilled. From the second distillation, the fraction which boiled between 70 C. and 130 C., vapor temperature, at 0.7 millimeter of mercury was retained and further distilled. The distillate collected from the second distillaion had a refractive index of 1.6585 at 25 C., indicating that it was neither monobromobenzene nor phosphorous trichloride which have refractive indices, respectively, of 1.5584 and 1.4600 at 25 C. From the third distillation the fraction which boiled between 110 C. and 122 C., vapor temperature, at a pressure of 0.7 millimeter of mercury was retained and further distilled. From the fourth distillation the fraction which boiled between 115 C. and 126 C., vapor temperature, at 1.0 millimeter of mercury was collected as product. The total weight of this fraction was 23.1 grams.

A microanalysis of the product was compared with the theoretical composition of monobromophenyl phosphorus thiodichloride, as indicated below:

6 bromophenyl phosphorous thiodichloride, were admixed with 11.7 grams (0.051 gram-mole) of 2,2-bis(4-hydroxyphenyl)propane in a glass vessel equipped with stirrer, thermometer, inert gas purge and reflux condenser.

The mixture was heated and stirred for 38 hours at atmospheric pressure, resulting in the evolution of hydrogen chloride gas. The temperature was elevated from 70 C. to 180 C. during this time.

For an additional 42 hours the mixture was heated and stirred at reduced pressure, 20 to 30 millimeters of mercury. Hyhdrogen chloride gas continued to evolve and the temperature was elevated to 200 C. The heating was then discontinued and the reaction product was allowed to cool.

The solid reaction product was solubilized with a solution of acetone and toluene, and vacuum filtered using a filter aid. The solvent was removed by vacuum distillation and evaporation in a vacuum oven at 90 C. for 12 hours. Eighteen and four-tenths (18.4) grams of brittle, resinous product were obtained. The product had a melting point of 121 C. and was liquid and flowing at 140 C.

Example V The following ingredients were admixed in a flask equipped with a stirrer, thermometer, and condenser:

Grams o-Dichlorobenzene 1.0 gram-mole) 147.0 Phosphorous trichloride (3.0 gram-moles) 413.0 Aluminum chloride (1.1 gram-moles) 146.6

The above mixture was agitated and heated at reflux temperature, about 85 C. for about 5 hours. Hydrogen chloride gas rapidly evolved during this period. The resulting mixture was cooled to approximately 30 C. and 33.6 grams of sulfur were added. The mixture exothermed to 64 C. The temperature of the mixture was raised to 80 C. and maintained there for a period of about 4 minutes.

The resulting mixture was distilled at reduced pressure and a pot temperature of 65 C. was maintained for 30 minutes to remove excess phosphorous trichloride, after which the residual aluminum chloride was removed by washing the distillant with ice water. The product was then extracted with monochlorobenzene. The monochlorobenzene solution was washed several times with water and subsequently phase-separated from the water.

The monochlorobenzene solvent was removed by distilling the solution obtained above at reduced pressure of 5 to 10 millimeters of mercury and a pot temperature of 80 C. Eighty three and three-tenths (83.3) grams of crude product were obtained.

The product was further purified by distillation, wherein the fraction boiling above 142 C., vapor temperature, at 1.9 millimeters of mercury, was retained and redistilled. From the second distillation the fraction which boiled between 132 C. and 136 C., vapor temperature, at 0.7 millimeter of mercury was retained and Percent Percent Percent Percent Percent Percent Carbon Hydrogen Chlorine Sulfur Phosphorous Bromine Theoretical Value 24. 85 1. 39 24. 46 11. 04 10. 68 27. 56 Experimental Value 24. 71 1. 37 24. 37 11. 05 10. 27. 73 Do 24. 78 1. 45 24. 46 11. 27 10. 59 27. 60

Example IV redistilled. From the third distillation the fraction which Sixteen and four-tenths (16.4) grams (0.057 gramboiled at 124 C., vapor temperature, at 0.5 millimeter mole) of the product of Example III, identified as monoof mercury, was collected as product.

A mi croanalysis of the product was compared with the theoretical composition of dichlorophenyl phosphorous thiodichloride, as indicated below:

tively, are combined with phosphorous trichloride and sulfur according to the method described in the above examples for the reaction of a halogenated mononuclear Percent Percent Percent Percent Percent Carbon Hydrogen Chlorine Phosphorous Sulfur Theoretical Value 25. 75 1. 08 50. 65 11. 07 11. 44 Experimental Value. 26. 02 1. 16 50. 77 11. 02 11. 44 Do 26. 04 1. 26 50. 93 11. 23 11. 59

Example VI aromatic hydrocarbon with phosphorous trichloride and Twenty eight and five-tenths (28.5) grams (0.10 grammole) of the product of Example V, identified as dichlorophenyl phosphorous thiodichloride, were admixed with 21.1 grams (0.09 gram-mole) of 2,2-bis(4-hydroxyphenyl)propane in a glass vessel equipped with stirrer, thermometer, inert gas purge and reflux condenser.

The mixture was heated and stirred for 40 hours at atmospheric pressure resulting in the rapid evolution of hydrogen chloride gas. The temperature was elevated from 135 C. to 184 C. during this time.

For an additional 36 hours the mixture was heated and stirred under reduced pressure, 10 millimeters of mercury to 2 millimeters of mercury. Hydrogen chloride gas continued to evolve and the temperature was elevated from 200 C. to 210 C. The heating was then discontinued and the reaction product was allowed to cool.

The solid reaction product was solubilized with toluene and filtered. The toluene solvent was evaporated leaving a solid resinous residue which Was melted and flowing at 173 C.

Example VII Phenyl phosphorous thiodichloride was prepared by the method outlined in Example I utilizing benzene, sulfur and phosphorous trichloride.

Example VIII Using the method outlined in Example II an interpolymer was prepared from phenyl phosphorous thiodichloride and 2,2-bis(4-hydroxyphenyl)propane.

Example IX The solid resinous products of Examples IV, VI and VIII were immersed in water at 70 C.76 C. for a period of hours. The water absorption was as follows.

Sample: Water absorption (percent) Example IV 1.48 Example VI 0.27 Example VIII 2.81

The halogenated phenyl phosphorous thiodichloride polymers exhibited a marked resistance to water absorption. This improved water-resistance is surprising as the increase in molecular weight of the polymer is slight in comparison with the relative increase in water resistance.

The excellent water resistance of the novel polymers described hereinabove make them especially suited for applications wherein poor water resistance is detrimental.

One such application is in the coatings field Where coatings, especially for wood surfaces, having poor water resistance are found to be susceptible to mildew.

Another use is in the manufacture of washaand-wem fabrics where it is very essential that the fabric be composed of fibers having excellent water resistance.

Other haloaryl phosphorous thiodichlorides, such as o-dibromophenyl phosphorous thiodichloride and monochlorotolyl phosphorous thiodichlorides are produced when o-dibromobenzene and monochlorotoluene, respecwherein X is a halogen radical selected from the class consisting of chlorine, bromine and fluorine, R is an alkyl group containing from about 1 to 6 carbon atoms, 12 is a whole number from 1 to 5, and m is a whole number less than 2 and including zero, and wherein the sum of m plus it does not exceed 5, and a non-adjacent polyhydroxy aromatic compound wherein the hydroxy groups are bonded directly to an aromatic nucleus.

2. The interpolymer of claim 1 wherein m equals zero. 3. The interpolymer of claim 1 wherein X is a chlorine radical. 4. The interpolymer of claim 1 wherein X is a bromine radical.

5. An interpolymer of a compound of the structure R Br 10. The copolymer of monochlorotolyl phosphonyl thiodichloride and 2,2-bis(4-hydroxypheny1)propane.

References Cited by the Examiner OTHER REFERENCES Denham et -a1.: 1. Organic Chemistry, vol. 23, pages 12981301 (1958), see Chem. Abs., v01. 53, 16036d (1959).

UNITED STATES PATENTS 5 Yagupolsk-ii: Chem. Abs., V01. 55, 22196f (1961). 12/1953 Jensen 260543 8/ 1959 Haven 2602 WILLIAM H. SHORT, Primary Examiner.

2/1960 McConnell 2602 7/1961 Rattenbury 260*543 J. R. LIBERMAN, Exammer.

3/ 1962 Groenweghe 260543 1 J. C. MARTIN, Assistant Examiner. 

1. AN INTERPOLYMER OF A COMPOUND OF THE STRUCTURE: 